CN104926961A - Preparation method of polyisoprene resin with low crystallinity - Google Patents
Preparation method of polyisoprene resin with low crystallinity Download PDFInfo
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- CN104926961A CN104926961A CN201510140447.3A CN201510140447A CN104926961A CN 104926961 A CN104926961 A CN 104926961A CN 201510140447 A CN201510140447 A CN 201510140447A CN 104926961 A CN104926961 A CN 104926961A
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- polyisoprene resin
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- polyisoprene
- crystallinity
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- -1 sulfur acyl chlorides Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 229920002449 FKM Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001774 Perfluoroether Polymers 0.000 description 4
- 241000907903 Shorea Species 0.000 description 4
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of a polyisoprene resin with low crystallinity. The polyisoprene resin with low crystallinity is a modified material synthesized by performing chlorosulfonation of molecular chains of the polyisoprene resin used as a raw material through a chlorosulfonation reagent in an organic solvent. The obtained polyisoprene resin modified material has the macromolecular chains introduced with strong polar groups, and the molecular chains of the material is reduced in crystallization ability, showing a good elasticity.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of polyisoprene resin chemical modification method.
Background technology
In recent years, the discovery of domestic TPI new synthetic process, makes TPI product be able to large-scale industrial production, supported titanium-AlR
3system catalysis isoprene bulk precipitation polymerization synthesis TPI greatly reduces the cost of TPI, for applying of TPI is laid a good foundation.Anti-form-1, easy crystallization under 4-polyisoprene normal temperature, hardness is high, dynamic heat build up is low, dynamic fatigue property is excellent.Because of its easy crystallization, can only be used as mechanically resistant material for a long time, emerge in large numbers around the discovery that the applied research of TPI is new in the recent period, its Application Areas is constantly expanded.TPI and other rubber blendings can significantly improve sizing material tensile modulus, reduce heat-dissipating, improve dynamic fatigue property.Therefore it is suitable in shock absorbing rubber product, but because of TPI low-temperature performance poor, severe cold area service requirements cannot be met.
The current approach improving low-temperature performance is primarily of following several: (1) changes molecular structure, the kindliness of molecular chain is changed by introducing the means such as flexible group, copolymerization, fundamentally solve winter hardiness problem, under making its low temperature, still keep favorable elasticity; (2) adopt the mode with the blend rubber of other low temperature performance excellents, by physically modified, break structural regularity, to obtain the blend compounds of high comprehensive performance; (3) select suitable vulcanization system, reinforcing filler in production process, add low temperature plasticizer to improve low-temperature performance (elastomerics, 2008,18 (2): 69-74).
Anti-form-1, the chemical modification mode of 4-polyisoprene has epoxidation trans-Isosorbide-5-Nitrae-polyisoprene and chlorination anti-form-1,4-polyisoprene at present, and gained derived products all makes some performance of TPI obtain the improvement of essence.Chlorosulfonation (Chlorosulfonation) is on organic molecule, introduce chlorosulfonyl (-SO
2cl) SULPHURYL CHLORIDE (R-SO is formed
2cl) process.Chlorosulphonation is a kind of substitution reaction, and a hydrogen atom in reactant is substituted by chlorosulfonyl.The chlorosulphonation of fatty compounds is generally with the mixed gas of sulfurous gas and chlorine or liquid sulfur acyl chlorides (SO
2cl
2) as chlorosulphonation reagent.The chlorosulphonation of aromatics (Ar-H) is then usual with chlorsulfonic acid (ClSO
3h) chlorosulphonation reagent.
Otazaghine B etc. has synthesized the different perfluoro methyl vinyl ether (PMVE) of a series of composition and vinylidene (VDF) copolymer, and compared for the low-temperature performance of multipolymer, find the increase along with vinylidene consumption, the second-order transition temperature of multipolymer reduces, when the molar fraction of vinylidene is 66.3%, multipolymer second-order transition temperature is-35.8 DEG C, and multipolymer second-order transition temperature is reduced to-41.4 DEG C of (European Polymer Joural when vinylidene molar fraction rises to 86.6%, 2005, 41 (8): 1747-1756).Abroad ether-containing key monomer (perfluoroalkyl vinyl ether class) is implanted in rubber macromolecule structure, is developed into fluoroether rubber, improves the kindliness of sizing material molecular chain, significantly improve sizing material low-temperature performance.Bian Jun peaks, Beijing Research Inst. of Aeronautic Material etc. are in viton and used a small amount of fluoroether rubber to develop viton FX-13, viton low-temperature performance is improved, its temperature limit of brittleness is low to moderate-45 DEG C, and this rubber price is compared fluoroether rubber and is greatly reduced (rubber industry, 2003,50 (1): 21-23).Fluoroether rubber on viton molecular chain, introduces perfluoroalkyl vinyl ether chain link and synthesizes, because the transposition of ehter bond inward turning is built lower than C-C singly-bound, improves the kindliness of molecular chain; In addition owing to instead of original-CF containing C-O group
2group, in molecule, the existence of O atom makes inter-molecular attraction effectively be reduced, thus improves the low-temperature flexibility of viton molecular chain.
This work adopts chlorosulphonation modification polyisoprene, introduces strong polar group, thus polyisoprene resin crystalline content is reduced, more easily keep good elasticity at low temperatures by polymer macromolecular chain.
Summary of the invention
The invention provides the polyisoprene modified material of a kind of low-crystallinity, it is characterized in that: described material modified be carry out modification by chlorosulphonation reagent, introduce strong polar group in polyisoprene macromolecular chain, crystalline content reduces, and more easily keeps good elasticity at low temperatures.
Present invention also offers the polyisoprene modified material preparation method of a kind of low-crystallinity, it is characterized in that: employing polyisoprene resin is raw material, by chlorosulphonation reagent in organic solvent, cause synthesis modification polyisoprene.First polyisoprene resin powder is added in there-necked flask, then organic solvent is injected by proportioning, stir and heat, treat that polyisoprene resin powder is fully dissolved in organic solution, 50 DEG C of constant temperature, logical nitrogen discharges the air in flask, adds quantitative initiator, then a certain amount of chlorosulphonation reagent is added, reaction times 1 ~ 4h.Cooling solution, then extracts with ethanol, product is placed in vacuum drying oven dry, obtains product.
Described polyisoprene modified material preparation method, chlorosulphonation reagent is selected from mixed gas or the liquid sulfur acyl chlorides of sulfurous gas and chlorine; Preferred SULPHURYL CHLORIDE (SO
2cl
2).
Described polyisoprene modified material preparation method, organic solvent is preferably chloroform.
Described polyisoprene modified material preparation method, initiator is preferably Diisopropyl azodicarboxylate (AIBN).
Embodiment
Below adopt embodiment to describe embodiments of the present invention in detail, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.
Embodiment 1
10g polyisoprene resin powder is added in 500ml there-necked flask, inject 200ml chloroform, stir and heat, treat that polyisoprene resin powder is fully dissolved in organic solution, 50 DEG C of constant temperature, logical nitrogen discharges the air in flask, adds 1g Diisopropyl azodicarboxylate, add 2ml SULPHURYL CHLORIDE, reaction times 1h.Cooling solution, then extracts with ethanol, product is placed in vacuum drying oven dry, obtains product.The data of sample test are as table 1:
Table 1 sample test experimental result
| Hardness (shoreA) | Tensile strength (MPa) | Melting enthalpy (J/g) | -60 DEG C of relative torsion modulus |
| 54 | 15.5 | 60.02 | 150 |
Embodiment 2
10g polyisoprene resin powder is added in 500ml there-necked flask, inject 200ml chloroform, stir and heat, treat that polyisoprene resin powder is fully dissolved in organic solution, 50 DEG C of constant temperature, logical nitrogen discharges the air in flask, adds 1g Diisopropyl azodicarboxylate, add 5ml SULPHURYL CHLORIDE, reaction times 1h.Cooling solution, then extracts with ethanol, product is placed in vacuum drying oven dry, obtains product.The data of sample test are as table 2:
Table 2 sample test experimental result
| Hardness (shoreA) | Tensile strength (MPa) | Melting enthalpy (J/g) | -60 DEG C of relative torsion modulus |
| 51 | 16.3 | 47.01 | 130 |
Embodiment 3
10g polyisoprene resin powder is added in 500ml there-necked flask, inject 200ml chloroform, stir and heat, treat that polyisoprene resin powder is fully dissolved in organic solution, 50 DEG C of constant temperature, logical nitrogen discharges the air in flask, adds 1g Diisopropyl azodicarboxylate, add 6ml SULPHURYL CHLORIDE, reaction times 1h.Cooling solution, then extracts with ethanol, product is placed in vacuum drying oven dry, obtains product.The data of sample test are as table 3:
Table 3 sample test experimental result
| Hardness (shoreA) | Tensile strength (MPa) | Melting enthalpy (J/g) | -60 DEG C of relative torsion modulus |
| 50 | 15.6 | 45.10 | 100 |
Embodiment 4
10g polyisoprene resin powder is added in 500ml there-necked flask, inject 200ml chloroform, stir and heat, treat that polyisoprene resin powder is fully dissolved in organic solution, 50 DEG C of constant temperature, logical nitrogen discharges the air in flask, adds 1g Diisopropyl azodicarboxylate, add 12ml SULPHURYL CHLORIDE, reaction times 1h.Cooling solution, then extracts with ethanol, product is placed in vacuum drying oven dry, obtains product.The data of sample test are as table 4:
Table 4 sample test experimental result
| Hardness (shoreA) | Tensile strength (MPa) | Melting enthalpy (J/g) | -60 DEG C of relative torsion modulus |
| 49.5 | 14.10 | 28.20 | 90 |
Claims (6)
1. the preparation method of a low-crystallinity polyisoprene resin, it is characterized in that: described material modified be carry out modification by chlorosulphonation reagent, introduce strong polar group by polyisoprene macromolecular chain, its crystalline content reduces, and more easily keeps good elasticity at low temperatures.
2. low-crystallinity polyisoprene resin according to claim 1, is characterized in that preparation method is as follows:
Employing polyisoprene resin is raw material, by chlorosulphonation reagent in organic solvent, causes synthesis low-crystallinity polyisoprene resin.First polyisoprene resin powder is added in there-necked flask, then organic solvent is injected by proportioning, stir and heat, treat that polyisoprene resin powder is fully dissolved in organic solution, 50 DEG C of constant temperature, logical nitrogen discharges the air in flask, adds quantitative initiator, then a certain amount of chlorosulphonation reagent is added, reaction times 1 ~ 4h.Cooling solution, extracts with ethanol, product is placed in vacuum drying oven dry, obtains product.
3. low-crystallinity polyisoprene resin preparation method as claimed in claim 2, is characterized in that: described chlorosulphonation reagent is selected from mixed gas or the liquid sulfur acyl chlorides of sulfurous gas and chlorine.
4. chlorosulphonation reagent according to claim 3, is characterized in that: preferably SULPHURYL CHLORIDE (SO
2cl
2).
5. low-crystallinity polyisoprene resin preparation method as claimed in claim 2, is characterized in that: described organic solvent is selected from the one in chloroform, hexanaphthene, acetone, wherein, is preferably chloroform.
6. low-crystallinity polyisoprene resin preparation method as claimed in claim 2, is characterized in that: described initiator is preferably Diisopropyl azodicarboxylate (AIBN).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130317176A1 (en) * | 2012-05-28 | 2013-11-28 | Beijing Research Institute Of Chemical Industry China Petroleum & Chemical Corporation | Polyisoprene, preparation method thereof, polyisoprene rubber compounds and vulcanizate therefrom |
| CN104004115A (en) * | 2014-04-29 | 2014-08-27 | 江苏瑞和新材料股份有限公司 | Preparation method of chlorosulfonated polyisoprene and preparation method thereof |
| CN105985472A (en) * | 2015-02-09 | 2016-10-05 | 中国石油化工股份有限公司 | Rare earth catalyst and preparation method thereof and polyisoprene preparation method |
-
2015
- 2015-03-27 CN CN201510140447.3A patent/CN104926961A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130317176A1 (en) * | 2012-05-28 | 2013-11-28 | Beijing Research Institute Of Chemical Industry China Petroleum & Chemical Corporation | Polyisoprene, preparation method thereof, polyisoprene rubber compounds and vulcanizate therefrom |
| CN103450378A (en) * | 2012-05-28 | 2013-12-18 | 中国石油化工股份有限公司 | Polyisoprene as well as preparation method thereof and polyisoprene rubber compound and vulcanized rubber |
| CN104004115A (en) * | 2014-04-29 | 2014-08-27 | 江苏瑞和新材料股份有限公司 | Preparation method of chlorosulfonated polyisoprene and preparation method thereof |
| CN105985472A (en) * | 2015-02-09 | 2016-10-05 | 中国石油化工股份有限公司 | Rare earth catalyst and preparation method thereof and polyisoprene preparation method |
Non-Patent Citations (3)
| Title |
|---|
| 周公度: "《大学化学词典》", 30 November 1992 * |
| 燕丰: "江苏瑞和新材料开发出制备氯磺化聚异戊二烯新方法", 《橡塑技术与装备》 * |
| 王潇: "反式-1,4-聚异戊二烯/天然橡胶并用胶的阻尼与低温性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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Application publication date: 20150923 |